Stabilizer mixtures

ABSTRACT

A stabilizer mixture containing (I) one low molecular weight alkylated sterically hindered amine compound; and (II) one high molecular weight alkylated sterically hindered amine compound.

This is a Continuation of application Ser. No. 10/276,091, filed on Nov.11, 2002 and herein entirely incorporated by reference.

The present invention relates to a stabilizer mixture containing onespecific low molecular weight alkylated sterically hindered aminecompound and one specific high molecular weight alkylated stericallyhindered amine compound, the use of this mixture for stabilizing anorganic material, in particular a polyolefin, against degradationinduced by light, heat or oxidation and the organic material thusstabilized.

The stabilization of polyolefins is described in numerous publications,for example in U.S. Pat. No. 4,692,468, U.S. Pat. No. 4,863,981, U.S.Pat. No. 5,719,217, U.S. Pat. No. 6,015,849, U.S. Pat. No. 6,020,406,U.S. Pat. No. 5,965,643, U.S. Pat. No. 5,980,783, U.S. Pat. No.5,919,399, U.S. Pat. No. 5,817,821, U.S. Pat. No. 6,126,861 andEP-A-345,220. An UV light stabilization additive package for solar cellmodule and laminated glass applications is disclosed in WO-A-99/05,206.

In more detail, the present invention relates to

a stabilizer mixture containing

-   (I) one sterically hindered amine compound selected from the group    consisting of the classes (α-1), (α-2), (α-3), (α-4) and (α-5); and-   (II) one sterically hindered amine compound selected from the group    consisting of the classes (β-1), (β-2), (β-3) and (β-4);-   (α-1) a compound of the formula (A-1)    in which    E₁ is C₁-C₄alkyl,    m, is 1, 2 or 4,    if m₁ is 1, E₂ is C₁-C₂₅alkyl,    if m₁ is 2, E₂ is C₁-C₁₄alkylene or a group of the formula (a-I)    wherein E₃ is C₁-C₁₀alkyl or C₂-C₁₀alkenyl, E₄ is C₁-C₁₀alkylene,    and    E₅ and E₆ independently of one another are C₁-C₄alkyl, cyclohexyl or    methylcyclohexyl, and    if m₁ is 4, E₂ is C₄-C₁₀alkanetetrayl;    (α-2) a compound of the formula (A-2)    in which    two of the radicals E₇ are —COO—(C₁-C₂₀alkyl), and    two of the radicals E₇ are a group of the formula (a-II)    with E₈ having one of the meanings of E₁;    (α-3) a compound of the formula (A-3)    in which    E₉ is C₁-C₂₄alkyl, and    E₁₀ has one of the meanings of E₁;    (α-4) a compound of the formula (A-4)    wherein    the radicals E₁₁ independently of one another have one of the    meanings of E₁,    and E₁₂ is hydrogen, C₁-C₁₂alkyl or C₁-C₁₂alkoxy;    (α-5) a compound of the formula (A-5)    wherein    E₁₃ has one of the meanings of E₁, and    E₁₄ is a group of the formula (a-III)    wherein the radicals E₁₅ independently of one another are    C₂-C₁₂alkylene, and the radicals E₁₆ independently of one another    are C₁-C₁₂alkyl or C₅-C₁₂cycloalkyl;    (β-1) a compound of the formula (B-1)    in which    R₁, R₃, R₄ and R₅ independently of one another are hydrogen,    C₁-C₁₂alkyl, C₅-C₁₂cycloalkyl, C₁-C₄-alkyl-substituted    C₅-C₁₂cycloalkyl, phenyl, phenyl which is substituted by —OH and/or    C₁-C₁₀alkyl; C₇-C₉phenylalkyl, C₇-C₉phenylalkyl which is substituted    on the phenyl radical by —OH and/or C₁-C₁₀alkyl; or a group of the    formula (b-I)    R₂ is C₂-C₁₈alkylene, C₅-C₇cycloalkylene or    C₁-C₄alkylenedi(C₅-C₇cycloalkylene), or    the radicals R₁, R₂ and R₃, together with the nitrogen atoms to    which they are bonded, perform a 5- to 10-membered heterocyclic    ring, or    R₄ and R₅, together with the nitrogen atom to which they are bonded,    form a 5- to 10-membered heterocyclic ring,    R₆ is C₁-C₄alkyl, and    b₁ is a number from 2 to 50,    with the proviso that at least one of the radicals R₁, R₃, R₄ and R₅    is a group of the formula (b-I);    (β-2) a compound of the formula (B-2)    wherein    R₇ and R₁₁, independently of one another are hydrogen or    C₁-C₁₂alkyl,    R₈, R₉ and R₁₀ independently of one another are C₂-C₁₀alkylene, and    X₁, X₂, X₃, X₄, X₅, X₆, X₇ and X₈ independently of one another are a    group of the formula (b-II),    in which R₁₂ is hydrogen, C₁-C₁₂alkyl, C₅-C₁₂cycloalkyl,    C₁-C₄alkyl-substituted C₅-C₁₂cycloalkyl, phenyl, —OH— and/or    C₁-C₁₀alkyl-substituted phenyl, C₇-C₉phenylalkyl, C₇-C₉phenylalkyl    which is substituted on the phenyl radical by —OH and/or    C₁-C₁₀alkyl; or a group of the formula (b-I) as defined above, and    R₁₃ has one of the meanings of R₆;    (β-3) a compound of the formula (B-3)    in which    R₁₄, R₁₅, R₁₆, R₁₇ and R₁₈ independently of one another are a direct    bond or C₁-C₁₀alkylene,    R₁₉ has one of the meanings of R₆, and    b₂ is a number from 1 to 50;    (β-4) a product (B-4) obtainable by reacting a product, obtained by    reaction of a polyamine of the formula (B-4-1) with cyanuric    chloride, with a compound of the formula (B-4-2)    in which    b′₃, b″₃ and b′″₃ independently of one another are a number from 2    to 12,    R₂₀ is hydrogen, C₁-C₁₂alkyl, C₅-C₁₂cycloalkyl, phenyl or    C₇-C₉phenylalkyl, and    R₂, has one of the meanings of R₆.

Examples of alkyl having up to 25 carbon atoms are methyl, ethyl,propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl,2-ethylbutyl, n-pentyl, isopentyl, 1-methylpentyl, 1,3-dimethyl-butyl,n-hexyl, 1-methylhexyl, n-heptyl, isoheptyl, 1,1,3,3-tetramethylbutyl,1-methylheptyl, 3-methylheptyl, n-octyl, 2-ethylhexyl,1,1,3-trimethylhexyl, 1,1,3,3-tetramethylpentyl, nonyl, decyl, undecyl,1-methylundecyl, dodecyl, 1,1,3,3,5,5-hexamethylhexyl, tridecyl,tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, eicosyl anddocosyl. E₁, E₈, E₁₀, E₁₁, E₁₃, R₆, R₁₃, R₁₉ and R₂, are preferablymethyl. R₂₀ is preferably butyl.

Examples of alkoxy having up to 12 carbon atoms are methoxy, ethoxy,propoxy, isopropoxy, butoxy, isobutoxy, pentoxy, isopentoxy, hexoxy,heptoxy, octoxy, decyloxy and dodecyloxy.

Examples of C₅-C₁₂cycloalkyl are cyclopentyl, cyclohexyl, cycloheptyl,cyclooctyl and cyclododecyl. C₅-C₈Cycloalkyl, especially cyclohexyl, ispreferred.

C₁-C₄Alkyl-substituted C₅-C₁₂cycloalkyl is for example methylcyclohexylor dimethylcyclohexyl.

—OH— and/or C₁-C₁₀alkyl-substituted phenyl is for example methylphenyl,dimethylphenyl, trimethylphenyl, tert-butylphenyl or3,5-di-tert-butyl-4-hydroxyphenyl.

Examples of C₇-C₉phenylalkyl are benzyl and phenylethyl.

C₇-C₉Phenylalkyl which is substituted on the phenyl radical by —OHand/or by alkyl having up to 10 carbon atoms is for examplemethylbenzyl, dimethylbenzyl, trimethylbenzyl, tert-butylbenzyl or3,5-di-tert-butyl-4-hydroxybenzyl.

Examples of alkenyl having up to 10 carbon atoms are allyl, 2-methallyl,butenyl, pentenyl and hexenyl. Allyl is preferred. The carbon atom inposition 1 is preferably saturated.

Examples of alkylene having up to 18 carbon atoms are methylene,ethylene, propylene, trimethylene, tetramethylene, pentamethylene,2,2-dimethyltrimethylene, hexamethylene, trimethylhexamethylene,octamethylene and decamethylene.

An example of C₄-C₁₀alkanetetrayl is 1,2,3,4-butanetetrayl.

An example of C₅-C₇cycloalkylene is cyclohexylene.

An example of C₁-C₄alkylenedi(C₅-C₇cycloalkylene) ismethylenedicyclohexylene.

Where the radicals R₁, R₂ and R₃, together with the nitrogen atoms towhich they are attached, form a 5- to 10-membered heterocyclic ring,this ring is for example

A 6-membered heterocyclic ring is preferred.

Where the radicals R₄ and R₅, together with the nitrogen atom to whichthey are attached, form a 5- to 10-membered heterocyclic ring, this ringis for example 1-pyrrolidyl, piperidino, morpholino, 1-piperazinyl,4-methyl-1-piperazinyl, 1-hexahydroazepinyl,5,5,7-trimethyl-1-homopiperazinyl or4,5,5,7-tetramethyl-1-homopiperazinyl. Morpholino is particularlypreferred.

R₁₅ is preferably a direct bond.

b₁ is preferably a number from 2 to 25, in particular 2 to 20.

b₂ is preferably a number from 1 to 25, in particluar 1 to 20.

b′₃ and b′″₃ are preferably 3 and b″₃ is preferably 2.

The compounds described above as components (I) and (II) are essentiallyknown. Most of them are commercially available. All of them can beprepared by known processes.

The preparation of the compounds of component (I) is disclosed, forexample, in U.S. Pat. No. 5,679,733, U.S. Pat. No. 3,640,928, U.S. Pat.No. 4,198,334, U.S. Pat. No. 4,619,958, U.S. Pat. No. 4,619,956,GB-A-2,269,819 and U.S. Pat. No. 5,071,981.

The preparation of the compounds of component (II) is disclosed, forexample, in U.S. Pat. No. 4,086,204, U.S. Pat. No. 6,046,304, U.S. Pat.No. 4,331,586, U.S. Pat. No. 4,108,829, U.S. Pat. No. 4,529,760 and U.S.Pat. No. 4,477,615.

The product (B-4) can be prepared analogously to known processes, forexample by reacting a polyamine of formula (B-4-1) with cyanuricchloride in a molar ratio of from 1:2 to 1:4 in the presence ofanhydrous lithium carbonate, sodium carbonate or potassium carbonate inan organic solvent such as 1,2-dichloroethane, toluene, xylene, benzene,dioxane or tert-amyl alcohol at a temperature of from −20° C. to +10°C., preferably from −10° C. to +10° C., in particular from 0° C. to +10°C., for from 2 to 8 hours, followed by reaction of the resultant productwith a 2,2,6,6-tetramethyl-4-piperidylamine of the formula (B-4-2). Themolar ratio of the 2,2,6,6-tetramethyl-4-piperidylamine to polyamine ofthe formula (B-4-1) employed is for example from 4:1 to 8:1. Thequantity of the 2,2,6,6-tetramethyl-4-piperidylamine can be added in oneportion or in more than one portion at intervals of a few hours.

The molar ratio of polyamine of the formula (B-4-1) to cyanuric chlorideto 2,2,6,6-tetramethyl-4-piperidylamine of the formula (B-4-2) ispreferably from 1:3:5 to 1:3:6.

The following example indicates one way of preparing the preferredproduct (B-4-a).

Example: 23.6 g (0.128 mol) of cyanuric chloride, 7.43 g (0.0426 mol) ofN,N′-bis[3-aminopropyl]ethylenediamine and 18 g (0.13 mol) of anhydrouspotassium carbonate are reacted at 5° C. for 3 hours with stirring in250 ml of 1,2-dichloroethane. The mixture is warmed at room temperaturefor a further 4 hours. 29.0 g (0.128 mol) ofN-(1,2,2,6,6-pentamethyl-4-piperidyl)butylamine are added and theresultant mixture is warmed at 60° C. for 2 hours. A further 18 g (0.13mol) of anhydrous potassium carbonate are added and the mixture iswarmed at 60° C. for a further 6 hours. The solvent is removed bydistillation under a slight vacuum (200 mbar) and replaced by xylene.19.4 g (0.085 mol) of N-(1,2,2,6,6-penta-methyl-4-piperidyl)butylamineand 5.2 g (0.13 mol) of ground sodium hydroxide are added, the mixtureis heated at reflux for 2 hours and, for a further 12 hours, the waterformed during the reaction is removed by azeotropic distillation. Themixture is filtered. The solution is washed with water and dried overNa₂SO₄. The solvent is evaporated and the residue is dried at 120-130°C. in vacuo (0.1 mbar). The desired product is obtained as a colourlessresin.

In general, the product (B-4) can, for example, be represented by acompound of the formula (B-4-α), (B-4-β) or (B-4-γ). It can also be inthe form of a mixture of these three compounds.

A preferred meaning of the formula (B-4-α) is

A preferred meaning of the formula (B-4-β) is

A preferred meaning of the formula (B-4-γ) is

In the above formulae (B-4-α) to (B-4-γ), b₃ is preferably 2 to 20, inparticular 2 to 10.

The sterically hindered amine compound of component (I) is preferablyselected from the group consisting of the following commercial products:

TINUVIN 765 (RTM), TINUVIN 144 (RTM), ADK STAB LA-52 (RTM), ADK STABLA-62 (RTM), SANDUVOR 3056 (RTM), SANDUVOR PR 31 (RTM) and GOODRITE UV3159 (RTM).

The N-methylated form (methylation of the nitrogen in the2,2,6,6-tetramethyl-4-piperidinyl group) of the commercial productDASTIB 845 (RTM) can easily be obtained by known processes for examplein analogy to the method described in U.S. Pat. No. 6,046,304, Example2. The compound so obtained is also preferably used as component (I).

The sterically hindered amine compound of component (II) is preferablyselected from the group consisting of the following commercial products:

CYASORB UV 3529 (RTM), CHIMASSORB 119 (RTM) and ADK STAB LA-63 (RTM).

The N-methylated form (methylation of the nitrogen in the2,2,6,6-tetramethyl-4-piperidinyl group) of the commercial productsCHIMASSORB 944 (RTM), CHIMASSORB 2020 (RTM) and UVASORB HA 88 (RTM) canalso easily be obtained by known processes for example in analogy to thesame method as described above. The compounds so obtained are likewisepreferably used as component (II).

The meanings of the terminal groups which saturate the free valences inthe compounds of the formulae (B-1), (B-3), (B-4-α), (B-4-β) and (B-4γ)depend on the processes used for their preparation. The terminal groupscan also be modified after the preparation of the compounds.

If the compounds of the formula (B-1) are prepared by reacting acompound of the formula

in which X is, for example, halogen, in particular chlorine, and R₄ andR₅ are as defined above, with a compound of the formula

in which R₁, R₂ and R₃ are as defined above, the terminal group bondedto the diamino radical is hydrogen or

and the terminal group bonded to the triazine radical is X or

If X is halogen, it is advantageous to replace this, for example, by —OHor an amino group when the reaction is complete. Examples of aminogroups which may be mentioned are pyrrolidin-1-yl, morpholino, —NH₂,—N(C₁-C₈)alkyl)₂ and —NR(C₁-C₈alkyl), in which R is hydrogen or a groupof the formula (b-I).

The compounds of the formula (B-1) also cover compounds of the formula

wherein R₁, R₂, R₃, R₄, R₅ and b₁ are as defined above and R₄* has oneof the meanings of R₄ and R₅* has one of the meanings of R₅.

One of the particularly preferred compounds of the formula (B-1) is

The preparation of this compound is generically described e.g. in U.S.Pat. No. 6,046,304.

In the compounds of the formula (B-3), the terminal group bonded to thecarbonyl radical is, for example,

and the terminal group bonded to the oxygen radical is, for example,

In the compounds of the formulae (B-4-α), (B-4-β) and (B-4-γ), theterminal group bonded to the triazine radical is, for example, Cl or a

group, and the terminal group bonded to the amino radical is, forexample, hydrogen or a

group.

A preferred stabilizer mixture is one wherein

component (I) is selected from class (α-1) and component (II) isselected from class (β-1); or

component (I) is selected from class (α-1) and component (II) isselected from class (β-2); or

component (I) is selected from class (α-1) and component (II) isselected from class (β-3); or

component (I) is selected from class (α-1) and component (II) isselected from class (β-4); or

component (I) is selected from class (α-2) and component (II) isselected from class (β-1); or

component (I) is selected from class (α-2) and component (II) isselected from class (β-2); or

component (I) is selected from class (α-2) and component (II) isselected from class (β-3); or

component (I) is selected from class (α-2) and component (II) isselected from class (β-4); or

component (I) is selected from class (α-3) and component (II) isselected from class (β-1); or

component (I) is selected from class (α-3) and component (II) isselected from class (β-2); or

component (i) is selected from class (α-3) and component (II) isselected from class (β-3); or

component (I) is selected from class (α-3) and component (II) isselected from class (β-4); or

component (I) is selected from class (α-4) and component (II) isselected from class (β-1); or

component (I) is selected from class (α-4) and component (II) isselected from class (β-2); or

component (I) is selected from class (α-4) and component (II) isselected from class (β-3); or

component (I) is selected from class (α-4) and component (II) isselected from class (β-4); or

component (i) is selected from class (α-5) and component (II) isselected from class (β-1); or

component (I) is selected from class (α-5) and component (II) isselected from class (β-2); or

component (I) is selected from class (α-5) and component (II) isselected from class (β-3); or

component (I) is selected from class (α-5) and component (II) isselected from class (β-4).

According to a preferred embodiment,

m₁ is 1, 2 or 4,

if m₁ is 1, E₂ is C₁₂-C₂₀alkyl,

if m₁ is 2, E₂ is C₂-C₁₀alkylene or a group of the formula (a-I)

E₃ is C₁-C₄alkyl,

E₄ is C₁-C₆alkylene, and

E₅ and E₆ independently of one another are C₁-C₄alkyl, and

if m₁ is 4, E₂ is C₄-C₈alkanetetrayl;

two of the radicals E₇ are —COO—(C₁₀-C₁₅alkyl), and

two of the radicals E₇ are a group of the formula (a-II);

E₉ is C₁₀-C₁₄alkyl;

E₁₂ is C₁-C₄alkoxy;

the radicals E₁₅ independently of one another are C₂-C₆alkylene, and

the radicals E₁₆ independently of one another are C₁-C₄alkyl orC₅-C₈cycloalkyl;

R₁ and R₃ independently of one another are a group of the formula (b-I),

R₂ is C₂-C₈alkylene,

R₄ and R₅ independently of one another are hydrogen, C₁-C₁₂alkyl,C₅-C₈cycloalkyl or a group of the formula (b-I), or the radicals R₄ andR₅, together with the nitrogen atom to which they are bonded, form a 5-to 10-membered heterocyclic ring, and

b₁ is a number from 2 to 25;

R₇ and R₁₁ independently of one another are hydrogen or C₁-C₄alkyl,

R₈, R₉ and R₁₀ independently of one another are C₂-C₄alkylene, and

X₁, X₂, X₃, X₄, X₅, X₆, X₇ and X₈ independently of one another are agroup of the formula (b-II),

R₁₂ is hydrogen, C₁-C₄alkyl, C₅-C₈cycloalkyl or a group of the formula(b-I);

R₁₄, R₁₅, R₁₆, R₁₇ and R₁₈ independently of one another are a directbond or

C₁-C₄alkylene, and

b₂ is a number from 1 to 25;

b′₃, b″₃ and b′″₃ independently of one another are a number from 2 to 4,and

R₂₀ is hydrogen, C₁-C₄alkyl, C₅-C₈cycloalkyl, phenyl or benzyl.

A further preferred embodiment corresponds to

a stabilizer mixture, wherein

component (I) is a compound of the formula (A-1-a), (A-1-b), (A-1-c),(A-1-d), (A-2-a), (A-3-a), (A-4-a) or (A-5-a); and

component (II) is a compound of the formula (B-1-a), (B-1-b), (B-1-c),(B-2-a), (B-3-a) or a product (B-4-a);

in which two of the radicals E₇ are —COO—C₁₃H₂₇ andtwo of the radicals E₇ are

wherein b₁ is a number from 2 to 20;

wherein b₂ is a number from 1 to 20;a product (B-4-a) obtainable by reacting a product, obtained by reactionof a polyamine of the formula (B-4-2-1-a) with cyanuric chloride, with acompound of the formula (B-4-2-a).

Component (I) is preferably the compound of the formula (A-1-a),(A-1-b), (A-1-c), (A-1-d), (A-2-a), (A-3-a), (A-4-a) or (A-5-a); and

component (II) is preferably the compound of the formula (B-1-c) or(B-2-a).

Component (I) is in particular the compound of the formula (A-1-b) andcomponent (II) is in particular the compound of the formula (B-1-c) or(B-2-a).

Preferred examples of stabilizer mixtures according to the presentinvention are:

1. Compound of the formula (A-1-a)+CHIMASSORB 119 (RTM)

2. TINUVIN 765 (RTM)+CHIMASSORB 119 (RTM)

3. TINUVIN 144 (RTM)+CHIMASSORB 119 (RTM)

4. ADK STAB LA-52 (RTM)+CHIMASSORB 119 (RTM)

5. ADK STAB LA-62 (RTM)+CHIMASSORB 119 (RTM)

6. SANDUVOR 3056 (RTM)+CHIMASSORB 119 (RTM)

7. SANDUVOR PR 31 (RTM)+CHIMASSORB 119 (RTM)

8. GOODRITE UV 3159 (RTM)+CHIMASSORB 119 (RTM)

9. Compound of the formula (A-1-a)+CYASORB UV 3529 (RTM)

10. TINUVIN 765 (RTM)+CYASORB UV 3529 (RTM)

11. TINUVIN 144 (RTM)+CYASORB UV 3529 (RTM)

12. ADK STAB LA-52 (RTM)+CYASORB UV 3529 (RTM)

13. ADK STAB LA-62 (RTM)+CYASORB UV 3529 (RTM)

14. SANDUVOR 3056 (RTM)+CYASORB UV 3529 (RTM)

15. SANDUVOR PR 31 (RTM)+CYASORB UV 3529 (RTM)

16. GOODRITE UV 3159 (RTM)+CYASORB UV 3529 (RTM)

17. Compound of the formula (A-1-a)+ADK STAB LA-63 (RTM)

18. TINUVIN 765 (RTM)+ADK STAB LA-63 (RTM)

19. TINUVIN 144 (RTM)+ADK STAB LA-63 (RTM)

20. ADK STAB LA-52 (RTM)+ADK STAB LA-63 (RTM)

21. ADK STAB LA-62 (RTM)+ADK STAB LA-63 (RTM)

22. SANDUVOR 3056 (RTM)+ADK STAB LA-63 (RTM)

23. SANDUVOR PR 31 (RTM)+ADK STAB LA-63 (RTM)

24. GOODRITE UV 3159 (RTM)+ADK STAB LA-63 (RTM)

25. Compound of the formula (A-1-a)+Compound of the formula (B-1-a)

26. TINUVIN 765 (RTM)+Compound of the formula (B-1-a)

27. TINUVIN 144 (RTM)+Compound of the formula (B-1-a)

28. ADK STAB LA-52 (RTM)+Compound of the formula (B-1-a)

29. ADK STAB LA-62 (RTM)+Compound of the formula (B-1-a)

30. SANDUVOR 3056 (RTM)+Compound of the formula (B-1-a)

31. SANDUVOR PR 31 (RTM)+Compound of the formula (B-1-a)

32. GOODRITE UV 3159 (RTM)+Compound of the formula (B-1-a)

33. Compound of the formula (A-1-a)+Compound of the formula (B-1-b)

34. TINUVIN 765 (RTM)+Compound of the formula (B-1-b)

35. TINUVIN 144 (RTM)+Compound of the formula (B-1-b)

36. ADK STAB LA-52 (RTM)+Compound of the formula (B-1-b)

37. ADK STAB LA-62 (RTM)+Compound of the formula (B-1-b)

38. SANDUVOR 3056 (RTM)+Compound of the formula (B-1-b)

39. SANDUVOR PR 31 (RTM)+Compound of the formula (B-1-b)

40. GOODRITE UV 3159 (RTM)+Compound of the formula (B-1-b)

41. Compound of the formula (A-1-a)+Product (B-4-a)

42. TINUVIN 765 (RTM)+Product (B-4-a)

43. TINUVIN 144 (RTM)+Product (B-4-a)

44. ADK STAB LA-52 (RTM)+Product (B-4-a)

45. ADK STAB LA-62 (RTM)+Product (B-4-a)

46. SANDUVOR 3056 (RTM)+Product (B-4-a)

47. SANDUVOR PR 31 (RTM)+Product (B-4-a)

48. GOODRITE UV 3159 (RTM)+Product (B-4-a)

The commercial product TINUVIN 765 (RTM) corresponds to the compound ofthe formula (A-1-b).

The commercial product TINUVIN 144 (RTM) corresponds to the compound ofthe formula (A-1-c).

The commercial product ADK STAB LA-52 (RTM) corresponds to the compoundof the formula (A-1-d).

The commercial product ADK STAB LA-62 (RTM) corresponds to the compoundof the formula (A-2-a).

The commercial product SANDUVOR 3056 (RTM) corresponds to the compoundof the formula (A-3-a).

The commercial product SANDUVOR PR 31 (RTM) corresponds to the compoundof the formula (A-4-a).

The commercial product GOODRITE UV 3159 (RTM) corresponds to thecompound of the formula (A-5-a).

The commercial product CHIMASSORB 119 (RTM) corresponds to the compoundof the formula (B-2-a).

The commercial product CYASORB UV 3529 (RTM) corresponds to the compoundof the formula (B-1-c).

The commercial product ADK STAB LA-63 (RTM) corresponds to the compoundof the formula (B-3-a).

A further preferred embodiment of this invention relates to a stabilizermixture containing additionally

(X-1) a pigment or

(X-2) an UV absorber or

(X-3) a pigment and an UV absorber.

The pigment (component (X-1)) may be an inorganic or organic pigment.

Examples of inorganic pigments are titanium dioxide, zinc oxide, carbonblack, cadmium sulfide, cadmium selenide, chromium oxide, iron oxide,lead oxide and so on.

Examples of organic pigments are azo pigments, anthraquinones,phthalocyanines, tetrachloroisoindolinones, quinacridones, isoindolines,perylenes, pyrrolopyrroles (such as Pigment Red 254) and so on.

All pigments described in “Gätchter/Müller: Plastics Additives Handbook,3rd Edition, Hanser Publishers, Munich Vienna N.Y.”, page 647 to 659,point 11.2.1.1 to 11.2.4.2 can be used as component (X-1).

A particularly preferred pigment is titanium dioxide, optionally incombination with an organic pigment.

Examples of such organic pigments are:

C.I. (Colour Index) Pigment Yellow 93, C.I. Pigment Yellow 95, C.I.Pigment Yellow 138, C.I. Pigment Yellow 139, C.I. Pigment Yellow 155,C.I. Pigment Yellow 162, C.I. Pigment Yellow 168, C.I. Pigment Yellow180, C.I. Pigment Yellow 183, C.I. Pigment Red 44, C.I. Pigment Red 170,C.I. Pigment Red 202, C.I. Pigment Red 214, C.I. Pigment Red 254, C.I.Pigment Red 264, C.I. Pigment Red 272, C.I. Pigment Red 48:2, C.I.Pigment Red 48:3, C.I. Pigment Red 53:1, C.I. Pigment Red 57:1, C.I.Pigment Green 7, C.I. Pigment Blue 15:1, C.I. Pigment Blue 15:3 and C.I.Pigment Violet 19.

Examples of the UV absorber (component (X-2)) are a2-(2′-hydroxyphenyl)benzotriazole, a 2-hydroxybenzophenone, an ester ofsubstituted or unsubstituted benzoic acid, an acrylate, an oxamide, a2-(2-hydroxyphenyl)-1,3,5-triazine, a monobenzoate of resorcinol or aformamidine.

The 2-(2′-hydroxyphenyl)benzotriazole is e.g.2-(2′-hydroxy-5′-methylphenyl)-benzotriazole,2-(3′,5′-di-tert-butyl-2′-hydroxyphenyl)benzotriazole,2-(5′-tert-butyl-2′-hydroxyphenyl)benzotriazole,2-(2′-hydroxy-5′-(1,1,3,3-tetramethylbutyl)phenyl)benzotriazole,2-(3′,5′-di-tert-butyl-2′-hydroxyphenyl)-5-chloro-benzotriazole,2-(3′-tert-butyl-2′-hydroxy-5′-methylphenyl)-5-chloro-benzotriazole,2-(3′-sec-butyl-5′-tert-butyl-2′-hydroxyphenyl)benzotriazole,2-(2′-hydroxy-4′-octyloxyphenyl)benzotriazole,2-(3′,5′-di-tert-amyl-2′-hydroxyphenyl)benzotriazole,2-(3′,5′-bis-(α,α-dimethylbenzyl)-2′-hydroxyphenyl)benzotriazole,mixture of2-(3′-tert-butyl-2′-hydroxy-5′-(2-octyloxycarbonylethyl)phenyl)-5-chloro-benzotriazole,2-(3′-tert-butyl-5′-[2-(2-ethylhexyloxy)-carbonylethyl]-2′-hydroxyphenyl)-5-chloro-benzotriazole,2-(3′-tert-butyl-2′-hydroxy-5′-(2-methoxycarbonylethyl)phenyl)-5-chloro-benzotriazole,2-(3′-tert-butyl-2′-hydroxy-5′-(2-methoxycarbonylethyl)phenyl)benzotriazole,2-(3′-tert-butyl-2′-hydroxy-5′-(2-octyloxycarbonylethyl)phenyl)benzotriazole,2-(3′-tert-butyl-5′-[2-(2-ethylhexyloxy)carbonylethyl]-2′-hydroxyphenyl)benzotriazole,2-(3′-dodecyl-2′-hydroxy-5′-methylphenyl)benzotriazole,2-(3′-tert-butyl-2′-hydroxy-5′-(2-isooctyloxycarbonylethyl)phenylbenzotriazole,2,2′-methylene-bis[4-(1,1,3,3-tetramethylbutyl)-6-benzotriazole-2-ylphenol]or the transesterification product of2-[3′-tert-butyl-5′-(2-methoxycarbonylethyl)-2′-hydroxyphenyl]-2H-benzotriazolewith polyethylene glycol 300; [R—CH₂CH₂—COO(CH₂)₃—]₂ whereR=3′-tert-butyl-4′-hydroxy-5′-2H-benzotriazol-2-ylphenyl.

2-(3′,5′-Di-tert-butyl-2′-hydroxyphenyl)-5-chloro-benzotriazole,2-(3′-tert-butyl-2′-hydroxy-5′-methylphenyl)-5-chloro-benzotriazole and2-(3′,5′-di-tert-amyl-2′-hydroxyphenyl)-benzotriazole are preferred.

The 2-hydroxybenzophenone is for example the 4-hydroxy, 4-methoxy,4-octyloxy, 4-decyloxy, 4-dodecyloxy, 4-benzyloxy, 4,2′,4′-trihydroxy or2′-hydroxy-4,4′-dimethoxy derivatives.

2-Hydroxy-4-octyloxybenzophenone is preferred.

The ester of a substituted or unsubstituted benzoic acid is for example4-tert-butyl-phenyl salicylate, phenyl salicylate, octylphenylsalicylate, dibenzoyl resorcinol, bis(4-tert-butylbenzoyl) resorcinol,benzoyl resorcinol, 2,4-di-tertbutylphenyl3,5-di-tert-butyl-4-hydroxybenzoate, hexadecyl3,5-di-tert-butyl-4-hydroxybenzoate, octadecyl3,5-di-tert-butyl-4-hydroxybenzoate or 2-methyl-4,6-di-tert-butylphenyl3,5-di-tert-butyl-4-hydroxybenzoate.

2,4-Di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate andhexadecyl 3,5-di-tert-butyl-4-hydroxybenzoate are preferred.

The acrylate is for example ethyl α-cyano-β,β-diphenylacrylate, isooctylα-cyano-β,β-diphenylacrylate, methyl α-carbomethoxycinnamate, methylα-cyano-β-methyl-β-methoxy-cinnamate, butylα-cyano-β-methyl-p-methoxy-cinnamate, methylα-carbomethoxy-p-methoxycinnamate orN-(β-carbomethoxy-β-cyanovinyl)-2-methylindoline.

The oxamide is for example 4,4′-dioctyloxyoxanilide,2,2′-diethoxyoxanilide, 2,2′-dioctyloxy-5,5′-di-tert-butoxanilide,2,2′-didodecyloxy-5,5′-di-tert-butoxanilide, 2-ethoxy-2′-ethyloxanilide,N,N′-bis(3-dimethylaminopropyl)oxamide,2-ethoxy-5-tert-butyl-2′-ethoxanilide or its mixture with2-ethoxy-2′-ethyl-5,4′-di-tert-butoxanilide or mixtures of ortho- andpara-methoxy-disubstituted oxanilides or mixtures of o- andp-ethoxy-disubstituted oxanilides.

The 2-(2-hydroxyphenyl)-1,3,5-triazine is for example2,4,6-tris(2-hydroxy-4-octyloxyphenyl)-1,3,5-triazine,2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2,4-bis(2-hydroxy-4-propyloxyphenyl)-6-(2,4-dimethylphenyl)-1,3,5-triazine,2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(4-methylphenyl)-1,3,5-triazine,2-(2-hydroxy-4-dodecyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2-(2-hydroxy-4-tridecyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2-[2-hydroxy-4-(2-hydroxy-3-butyloxy-propoxy)phenyl]-4,6-bis(2,4-dimethyl)-1,3,5-triazine,2-[2-hydroxy-4-(2-hydroxy-3-octyloxy-propyloxy)phenyl]4,6-bis(2,4-dimethyl)-1,3,5-triazine,2-[4-(dodecyloxy/tridecyloxy-2-hydroxypropoxy)-2-hydroxy-phenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2-[2-hydroxy-4-(2-hydroxy-3-dodecyloxy-propoxy)phenyl]-4,6-bis(2,4-dimethyl-phenyl)-1,3,5-triazine,2-(2-hydroxy-4-hexyloxy)phenyl-4,6-diphenyl-1,3,5-triazine,2-(2-hydroxy-4-methoxyphenyl)-4,6-diphenyl-1,3,5-triazine,2,4,6-tris[2-hydroxy-4-(3-butoxy-2-hydroxy-propoxy)phenyl]-1,3,5-triazineor 2-(2-hydroxyphenyl)-4-(4-methoxyphenyl)-6-phenyl-1,3,5-triazine.

2-(2-Hydroxy-4-octyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazineand 2-(2-hydroxy-4-hexyloxy)phenyl-4,6-diphenyl-1,3,5-triazine arepreferred.

The monobenzoate of resorcinol is for example the compound of theformula

The formamidine is for example the compound of the formula

The UV absorber is in particular a

2-(2′-hydroxyphenyl)benzotriazole, a 2-hydroxybenzophenone or ahydroxyphenyltriazine.

The stabilizer mixture according to this invention is suitable forstabilizing organic materials against degradation induced by light, heator oxidation. Examples of such organic materials are the following:

1. Polymers of monoolefins and diolefins, for example polypropylene,polyisobutylene, polybut-1-ene, poly-4-methylpent-1-ene, polyisoprene orpolybutadiene, as well as polymers of cycloolefins, for instance ofcyclopentene or norbornene, polyethylene (which optionally can becrosslinked), for example high density polyethylene (HDPE), high densityand high molecular weight polyethylene (HDPE-HMW), high density andultrahigh molecular weight polyethylene (HDPE-UHMW), medium densitypolyethylene (MDPE), low density polyethylene (LDPE), linear low densitypolyethylene (LLDPE), (VLDPE) and (ULDPE), or polyvinyl cyclohexane.

Polyolefins, i.e. the polymers of monoolefins exemplified in thepreceding paragraph, preferably polyethylene and polypropylene, can beprepared by different, and especially by the following, methods:

-   -   a) radical polymerisation (normally under high pressure and at        elevated temperature).    -   b) catalytic polymerisation using a catalyst that normally        contains one or more than one metal of groups IVb, Vb, VIb or        VIII of the Periodic Table. These metals usually have one or        more than one ligand, typically oxides, halides, alcoholates,        esters, ethers, amines, alkyls, alkenyls and/or aryls that may        be either π- or α-coordinated. These metal complexes may be in        the free form or fixed on substrates, typically on activated        magnesium chloride, titanium(III) chloride, alumina or silicon        oxide. These catalysts may be soluble or insoluble in the        polymerisation medium. The catalysts can be used by themselves        in the polymerisation or further activators may be used,        typically metal alkyls, metal hydrides, metal alkyl halides,        metal alkyl oxides or metal alkyloxanes, said metals being        elements of groups Ia, Ia and/or IIIa of the Periodic Table. The        activators may be modified conveniently with further ester,        ether, amine or silyl ether groups. These catalyst systems are        usually termed Phillips, Standard Oil Indiana, Ziegler (-Nafta),        TNZ (DuPont), metallocene or single site catalysts (SSC).

2. Mixtures of the polymers mentioned under 1), for example mixtures ofpolypropylene with polyisobutylene, polypropylene with polyethylene (forexample PP/HDPE, PP/LDPE) and mixtures of different types ofpolyethylene (for example LDPE/HDPE).

3. Copolymers of monoolefins and diolefins with each other or with othervinyl monomers, for example ethylene/propylene copolymers, linear lowdensity polyethylene (LLDPE) and mixtures thereof with low densitypolyethylene (LDPE), propylene/but-1-ene copolymers,propylene/isobutylene copolymers, ethylene/but-1-ene copolymers,ethylene/hexene copolymers, ethylene/methylpentene copolymers,ethylene/heptene copolymers, ethylene/octene copolymers,propylene/butadiene copolymers, isobutylene/isoprene copolymers,ethylene/alkyl acrylate copolymers, ethylene/alkyl methacrylatecopolymers, ethylene/vinyl acetate copolymers and their copolymers withcarbon monoxide or ethylene/acrylic acid copolymers and their salts(ionomers) as well as terpolymers of ethylene with propylene and a dienesuch as hexadiene, dicyclopentadiene or ethylidene-norbornene; andmixtures of such copolymers with one another and with polymers mentionedin 1) above, for example polypropylene/ethylene-propylene copolymers,LDPE/ethylene-vinyl acetate copolymers (EVA), LDPE/ethylene-acrylic acidcopolymers (EAA), LLDPE/EVA, LLDPE/EAA and alternating or randompolyalkylene/carbon monoxide copolymers and mixtures thereof with otherpolymers, for example polyamides.

4. Hydrocarbon resins (for example C₅-C₉) including hydrogenatedmodifications thereof (e.g. tackifiers) and mixtures of polyalkylenesand starch.

5. Polystyrene, poly(p-methylstyrene), poly(α-methylstyrene).

6. Copolymers of styrene or α-methylstyrene with dienes or acrylicderivatives, for example styrene/butadiene, styrene/acrylonitrile,styrene/alkyl methacrylate, styrene/butadiene/alkyl acrylate,styrene/butadiene/alkyl methacrylate, styrene/maleic anhydride,styrene/acrylonitrile/methyl acrylate; mixtures of high impact strengthof styrene copolymers and another polymer, for example a polyacrylate, adiene polymer or an ethylene/propylene/diene terpolymer; and blockcopolymers of styrene such as styrene/butadiene/styrene,styrene/isoprene/styrene, styrene/ethylene/butylene/styrene orstyrene/ethylene/propylene/styrene.

7. Graft copolymers of styrene or α-methylstyrene, for example styreneon polybutadiene, styrene on polybutadiene-styrene orpolybutadiene-acrylonitrile copolymers; styrene and acrylonitrile (ormethacrylonitrile) on polybutadiene; styrene, acrylonitrile and methylmethacrylate on polybutadiene; styrene and maleic anhydride onpolybutadiene; styrene, acrylonitrile and maleic anhydride or maleimideon polybutadiene; styrene and maleimide on polybutadiene; styrene andalkyl acrylates or methacrylates on polybutadiene; styrene andacrylonitrile on ethylene/propylene/diene terpolymers; styrene andacrylonitrile on polyalkyl acrylates or polyalkyl methacrylates, styreneand acrylonitrile on acrylate/butadiene copolymers, as well as mixturesthereof with the copolymers listed under 6), for example the copolymermixtures known as ABS, MBS, ASA or AES polymers.

8. Halogen-containing polymers such as polychloroprene, chlorinatedrubbers, chlorinated and brominated copolymer of isobutylene-isoprene(halobutyl rubber), chlorinated or sulfo-chlorinated polyethylene,copolymers of ethylene and chlorinated ethylene, epichlorohydrin homo-and copolymers, especially polymers of halogen-containing vinylcompounds, for example polyvinyl chloride, polyvinylidene chloride,polyvinyl fluoride, polyvinylidene fluoride, as well as copolymersthereof such as vinyl chloride/vinylidene chloride, vinyl chloride/vinylacetate or vinylidene chloride/vinyl acetate copolymers.

9. Polymers derived from α,β-unsaturated acids and derivatives thereofsuch as polyacrylates and polymethacrylates; polymethyl methacrylates,polyacrylamides and polyacrylonitriles, impact-modified with butylacrylate.

10. Copolymers of the monomers mentioned under 9) with each other orwith other unsaturated monomers, for example acrylonitrile/butadienecopolymers, acrylonitrile/alkyl acrylate copolymers,acrylonitrile/alkoxyalkyl acrylate or acrylonitrile/vinyl halidecopolymers or acrylonitrile/alkyl methacrylate/butadiene terpolymers.

11. Polymers derived from unsaturated alcohols and amines or the acylderivatives or acetals thereof, for example polyvinyl alcohol, polyvinylacetate, polyvinyl stearate, polyvinyl benzoate, polyvinyl maleate,polyvinyl butyral, polyallyl phthalate or polyallyl melamine; as well astheir copolymers with olefins mentioned in 1) above.

12. Homopolymers and copolymers of cyclic ethers such as polyalkyleneglycols, polyethylene oxide, polypropylene oxide or copolymers thereofwith bisglycidyl ethers.

13. Polyacetals such as polyoxymethylene and those polyoxymethyleneswhich contain ethylene oxide as a comonomer; polyacetals modified withthermoplastic polyurethanes, acrylates or MBS.

14. Polyphenylene oxides and sulfides, and mixtures of polyphenyleneoxides with styrene polymers or polyamides.

15. Polyurethanes derived from hydroxyl-terminated polyethers,polyesters or polybutadienes on the one hand and aliphatic or aromaticpolyisocyanates on the other, as well as precursors thereof.

16. Polyamides and copolyamides derived from diamines and dicarboxylicacids and/or from aminocarboxylic acids or the corresponding lactams,for example polyamide 4, polyamide 6, polyamide 6/6, 6/10, 6/9, 6/12,4/6, 12/12, polyamide 11, polyamide 12, aromatic polyamides startingfrom m-xylene diamine and adipic acid; polyamides prepared fromhexamethylenediamine and isophthalic or/and terephthalic acid and withor without an elastomer as modifier, for examplepoly-2,4,4,-trimethylhexamethylene terephthalamide or poly-m-phenyleneisophthalamide; and also block copolymers of the aforementionedpolyamides with polyolefins, olefin copolymers, ionomers or chemicallybonded or grafted elastomers; or with polyethers, e.g. with polyethyleneglycol, polypropylene glycol or polytetramethylene glycol; as well aspolyamides or copolyamides modified with EPDM or ABS; and polyamidescondensed during processing (RIM polyamide systems).

17. Polyureas, polyimides, polyamide-imides, polyetherimids,polyesterimids, polyhydantoins and polybenzimidazoles.

18. Polyesters derived from dicarboxylic acids and diols and/or fromhydroxycarboxylic acids or the corresponding lactones, for examplepolyethylene terephthalate, polybutylene terephthalate,poly-1,4-dimethylolcyclohexane terephthalate, polyalkylene naphthalate(PAN) and polyhydroxybenzoates, as well as block copolyether estersderived from hydroxyl-terminated polyethers; and also polyestersmodified with polycarbonates or MBS.

19. Polycarbonates and polyester carbonates.

20. Polysulfones, polyether sulfones and polyether ketones.

21. Crosslinked polymers derived from aldehydes on the one hand andphenols, ureas and melamines on the other hand, such asphenol/formaldehyde resins, urea/formaldehyde resins andmelamine/formaldehyde resins.

22. Drying and non-drying alkyd resins.

23. Unsaturated polyester resins derived from copolyesters of saturatedand unsaturated dicarboxylic acids with polyhydric alcohols and vinylcompounds as crosslinking agents, and also halogen-containingmodifications thereof of low flammability.

24. Crosslinkable acrylic resins derived from substituted acrylates, forexample epoxy acrylates, urethane acrylates or polyester acrylates.

25. Alkyd resins, polyester resins and acrylate resins crosslinked withmelamine resins, urea resins, isocyanates, isocyanurates,polyisocyanates or epoxy resins.

26. Crosslinked epoxy resins derived from aliphatic, cycloaliphatic,heterocyclic or aromatic glycidyl compounds, e.g. products of diglycidylethers of bisphenol A and bisphenol F, which are crosslinked withcustomary hardeners such as anhydrides or amines, with or withoutaccelerators.

27. Natural polymers such as cellulose, rubber, gelatin and chemicallymodified homologous derivatives thereof, for example cellulose acetates,cellulose propionates and cellulose butyrates, or the cellulose etherssuch as methyl cellulose; as well as rosins and their derivatives.

28. Blends of the aforementioned polymers (polyblends), for examplePP/EPDM, Polyamide/EPDM or ABS, PVC/EVA, PVC/ABS, PVC/MBS, PC/ABS,PBTP/ABS, PC/ASA, PC/PBT, PVC/CPE, PVC/acrylates, POM/thermoplastic PUR,PC/thermoplastic PUR, POM/acrylate, POM/MBS, PPO/HIPS, PPO/PA 6.6 andcopolymers, PA/HDPE, PA/PP, PA/PPO, PBT/PC/ABS or PBT/PET/PC.

29. Naturally occurring and synthetic organic materials which are puremonomeric compounds or mixtures of such compounds, for example mineraloils, animal and vegetable fats, oil and waxes, or oils, fats and waxesbased on synthetic esters (e.g. phthalates, adipates, phosphates ortrimellitates) and also mixtures of synthetic esters with mineral oilsin any weight ratios, typically those used as spinning compositions, aswell as aqueous emulsions of such materials.

30. Aqueous emulsions of natural or synthetic rubber, e.g. natural latexor latices of carboxylated styrene/butadiene copolymers.

This invention therefore additionally relates to a compositioncomprising an organic material subject to degradation induced by light,heat or oxidation and the stabilizer mixture described above.

A further embodiment of the present invention is a method forstabilizing an organic material against degradation induced by light,heat or oxidation, which comprises incorporating into the organicmaterial the stabilizer mixture described above.

The organic material is preferably a synthetic polymer, in particularfrom one of the above groups. Polyolefins are preferred andpolyethylene, polypropylene, a polyethylene copolymer or a polypropylenecopolymer are particularly preferred. Polypropylene containing talcand/or other fillers (e.g. CaCO₃) is also preferred. Pigmentedpolyolefins and pigmented polyamides are further preferred.Acrylonitrile/butadiene/styrene is also preferred as organic material.

The components (I), (II) and optionally (X-1) and/or (X-2) may be addedto the organic material to be stabilized either individually or mixedwith one another.

The total amount of the two sterically hindered amine compounds(components (I) and (II)) in the organic material to be stabilized ispreferably 0.005 to 5%, in particular 0.01 to 1% or 0.05 to 1%, relativeto the weight of the organic material.

The pigment (component (X-1)) is optionally present in the organicmaterial in an amount of preferably 0.01 to 10%, in particular 0.05 to1%, relative to the weight of the organic material.

The UV absorber (component (X-2)) is optionally present in the organicmaterial in an amount of preferably 0.01 to 1%, in particular 0.05 to0.5%, relative to the weight of the organic material.

The total amount of component (X-3) (the pigment in combination with theUV absorber) is preferably 0.01 to 10%, relative to the weight of theorganic material. The weight ratio of the UV absorber to the pigment isfor example 2:1 to 1:10.

When the pigment used is titanium dioxide in combination with an organicpigment as described above, titanium dioxide is preferably present inthe organic material in an amount of 0.01 to 5%, relative to the weightof the organic material, and the organic pigment may be present in anamount of, for example, 0.01 to 2%, relative to the weight of theorganic material.

The weight ratio of components (I):(II) is for example 1:10 to 10:1,preferably 1:5 to 5:1, in particular 1:2 to 2:1.

The weight ratio of the components (I) and (II):(X-1) is for example1:100 to 10:1, preferably 1:5 to 5:1, in particular 1:2 to 2:1.

The weight ratio of the components (I) and (II):(X-2) is for example 1:5to 20:1, preferably 1:2 to 2:1.

The weight ratio of the components (I) and (II):(X-3) is for example1:100 to 10:1, preferably 1:5 to 5:1, in particular 1:2 to 2:1.

The above components can be incorporated into the organic material to bestabilized by known methods, for example before or during shaping or byapplying the dissolved or dispersed compounds to the organic material,if necessary with subsequent evaporation of the solvent. The componentscan be added to the organic material in the form of a powder, granulesor a masterbatch, which contains these components in, for example, aconcentration of from 2.5 to 25% by weight.

If desired, the components (I) and (II) and optionally (X-1) and/or(X-2) can be melt blended with each other before incorporation in theorganic material. They can be added to a polymer before or during thepolymerization or before the crosslinking.

The materials stabilized according to this invention can be used in awide variety of forms, for example as films, fibres, tapes, mouldingcompositions, profiles or as binders for paints, adhesives or putties.

The stabilized material may additionally also contain variousconventional additives, for example:

1. Antioxidants

1.1. Alkylated monophenols, for example2,6-di-tert-butyl-4-methylphenol, 2-tert-butyl-4,6-dimethylphenol,2,6-di-tert-butyl-4-ethylphenol, 2,6-di-tert-butyl-4-n-butyl-phenol,2,6-di-tert-butyl-4-isobutylphenol, 2,6-dicyclopentyl-4-methylphenol,2-α-methylcyclohexyl)-4,6-dimethylphenol,2,6-dioctadecyl-4-methylphenol, 2,4,6-tri-cyclohexylphenol,2,6-di-tert-butyl-4-methoxymethylphenol, nonylphenols which are linearor branched in the side chains, for example,2,6-di-nonyl-4-methylphenol,2,4-dimethyl-6-(1′-methylundec-1′-yl)phenol,2,4-dimethyl-6-(1′-methylheptadec-1′-yl)phenol,2,4-dimethyl-6-(1′-methyltridec-1′-yl)phenol and mixtures thereof.

1.2. Alkylthiomethylphenols, for example2,4-dioctylthiomethyl-6-tert-butylphenol,2,4-dioctylthiomethyl-6-methylphenol,2,4-dioctylthiomethyl-6-ethylphenol,2,6-di-dodecylthiomethyl-4-nonylphenol.

1.3. Hydroquinones and alkylated hydroquinones, for example2,6-di-tert-butyl-4-methoxyphenol, 2,5-di-tert-butylhydroquinone,2,5-di-tert-amylhydroquinone, 2,6-diphenyl-4-octadecyloxyphenol,2,6-di-tert-butylhydroquinone, 2,5-di-tert-butyl-4-hydroxyanisole,3,5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tert-butyl-4-hydroxyphenylstearate, bis-(3,5-di-tert-butyl-4-hydroxyphenyl) adipate.

1.4. Tocopherols, for example α-tocopherol, β-tocopherol, γ-tocopherol,8-tocopherol and mixtures thereof (Vitamin E).

1.5. Hydroxylated thiodiphenyl ethers, for example2,2′-thiobis(6-tert-butyl-4-methylphenol), 2,2′-thiobis(4-octylphenol),4,4′-thiobis(6-tert-butyl-3-methylphenol),4,4′-thiobis(6-tert-butyl-2-methylphenol),4,4′-thiobis-(3,6-di-sec-amylphenol),4,4′-bis-(2,6-dimethyl-4-hydroxyphenyl) disulfide.

1.6. Alkylidenebisphenols, for example2,2′-methylenebis(6-tert-butyl-4-methylphenol),2,2′-methylenebis(6-tert-butyl-4-ethylphenol),2,2′-methylenebis[4-methyl-6-(α-methylcyclohexyl)phenol],2,2′-methylenebis(4-methyl-6-cyclohexylphenol),2,2′-methylenebis(6-nonyl-4-methylphenol),2,2′-methylenebis(4,6-di-tert-butylphenol),2,2′-ethylidenebis(4,6-di-tert-butylphenol),2,2′-ethylidenebis(6-tert-butyl-4-isobutylphenol),2,2′-methylenebis[6-(α-methylbenzyl)-4-nonylphenol],2,2′-methylenebis[6-(α,α-dimethylbenzyl)-4-nonylphenol],4,4′-methylenebis(2,6-di-tert-butylphenol),4,4′-methylenebis(6-tert-butyl-2-methylphenol),1,1-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)butane,2,6-bis(3-tert-butyl-5-methyl-2-hydroxybenzyl)-4-methylphenol,1,1,3-tris(5-tert-butyl-4-hydroxy-2-methylphenyl)butane,1,1-bis(5-tert-butyl-4-hydroxy-2-methyl-phenyl)-3-n-dodecylmercaptobutane,ethylene glycol bis[3,3-bis(3′-tert-butyl-4′-hydroxyphenyl)butyrate],bis(3-tert-butyl-4-hydroxy-5-methyl-phenyl)dicyclopentadiene,bis[2-(3′-tert-butyl-2′-hydroxy-5′-methylbenzyl)-6-tert-butyl-4-methylphenyl]terephthalate,1,1-bis-(3,5-dimethyl-2-hydroxyphenyl)butane,2,2-bis-(3,5-di-tert-butyl-4-hydroxyphenyl)propane,2,2-bis-(5-tert-butyl-4-hydroxy2-methylphenyl)-4-n-dodecylmercaptobutane,1,1,5,5-tetra-(5-tert-butyl-4-hydroxy2-methylphenyl)pentane.

1.7. O-, N- and S-benzyl compounds, for example3,5,3′,5′-tetra-tert-butyl-4,4′-dihydroxydibenzyl ether,octadecyl-4-hydroxy-3,5-dimethylbenzylmercaptoacetate,tridecyl-4-hydroxy-3,5-di-tert-butylbenzylmercaptoacetate,tris(3,5-di-tert-butyl-4-hydroxybenzyl)amine,bis(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)dithioterephthalate,bis(3,5-di-tert-butyl-4-hydroxybenzyl)sulfide,isooctyl-3,5-di-tert-butyl-4-hydroxybenzylmercaptoacetate.

1.8. Hydroxybenzylated malonates, for exampledioctadecyl-2,2-bis-(3,5-di-tert-butyl-2-hydroxybenzyl)-malonate,di-octadecyl-2-(3-tert-butyl-4-hydroxy-5-methylbenzyl)-malonate,di-dodecylmercaptoethyl-2,2-bis-(3,5-di-tert-butyl-4-hydroxybenzyl)malonate,bis[4-(1,1,3,3-tetramethylbutyl)phenyl]-2,2-bis(3,5-di-tert-butyl-4-hydroxybenzyl)malonate.

1.9. Aromatic hydroxybenzyl compounds, for example1,3,5-tris-(3,5-di-tert-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene,1,4-bis(3,5-di-tert-butyl-4-hydroxybenzyl)-2;3,5,6-tetramethylbenzene,2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)phenol.

1.10. Triazine Compounds, for example2,4-bis(octylmercapto)-6-(3,5-di-tert-butyl-4-hydroxyanilino)-1,3,5-triazine,2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyanilino)-1,3,5-triazine,2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyphenoxy)-1,3,5-triazine,2,4,6-tris(3,5-di-tert-butyl-4-hydroxyphenoxy)-1,2,3-triazine,1,3,5-tris-(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate,1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)isocyanurate,2,4,6-tris(3,5-di-tert-butyl-4-hydroxyphenylethyl)-1,3,5-triazine,1,3,5-tris(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)-hexahydro-1,3,5-triazine,1,3,5-tris(3,5-dicyclohexyl-4-hydroxybenzyl)isocyanurate.

1.11. Benzylphosphonates, for exampledimethyl-2,5-di-tert-butyl-4-hydroxybenzyl-phosphonate,diethyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate,dioctadecyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate,dioctadecyl-5-tert-butyl-4-hydroxy3-methylbenzylphosphonate, the calciumsalt of the monoethyl ester of3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid.

1.12. Acylaminophenols, for example 4-hydroxylauranilide,4-hydroxystearanilide, octylN-(3,5-di-tert-butyl-4-hydroxyphenyl)carbamate.

1.13. Esters of D-(3,5-di-tert-butyl-4-hydroxyphenyl)proiionic acid withmono- or polyhydric alcohols, e.g. with methanol, ethanol, n-octanol,i-octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol,1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethyleneglycol, triethylene glycol, pentaerythritol, tris-(hydroxyethyl)isocyanurate, N,N′-bis(hydroxyethyl)oxamide, 3-thiaundecanol,3-thiapentadecanol, trimethylhexanediol, trimethylolpropane,4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.

1.14. Esters of D-(5-tert-butyl-4-hydroxy-3-methylphenyl)propionic acidwith mono- or polyhydric alcohols, e.g. with methanol, ethanol,n-octanol, i-octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol,ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethyleneglycol, diethylene glycol, triethylene glycol, pentaerythritol,tris(hydroxyethyl) isocyanurate, N,N′-bis(hydroxyethyl)oxamide,3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol,trimethylolpropane,4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.

1.15. Esters of β-(3,5-dicyclohexyl-4-hydroxyphenyl)propionic acid withmono- or polyhydric alcohols, e.g. with methanol, ethanol, octanol,octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol,1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethyleneglycol, triethylene glycol, pentaerythritol,tris-(hydroxyethyl)isocyanurate, N,N′-bis(hydroxyethyl)oxamide,3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol,trimethylolpropane,4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.

1.16. Esters of 3,5-di-tert-butyl-4-hydroxyphenyl acetic acid with mono-or polyhydric alcohols, e.g. with methanol, ethanol, octanol,octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol,1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethyleneglycol, triethylene glycol, pentaerythritol,tris-(hydroxyethyl)isocyanurate, N,N′-bis(hydroxyethyl)oxamide,3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol,trimethylolpropane,4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.

1.17. Amides of β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid e.g.N,N′-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hexamethylenediamine,N,N′-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)trimethylenediamine,N,N′-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hydrazine.

1.18. Ascorbic acid (vitamin C)

1.19. Aminic antioxidants, for exampleN,N′-di-isopropyl-p-phenylenediamine,N,N′-di-sec-butyl-p-phenylenediamine,N,N′-bis(1,4-dimethylpentyl)-p-phenylenediamine,N,N′-bis(1-ethyl-3-methylpentyl)-p-phenylenediamine,N,N′-bis(1-methylheptyl)-p-phenylenediamine,N,N′-dicyclohexyl-p-phenylenediamine, N,N′-diphenyl-p-phenylenediamine,N,N′-bis(2-naphthyl)-p-phenylenediamine,N-isopropyl-N′-phenyl-p-phenylenediamine,N-(1,3-dimethylbutyl)-N′-phenyl-p-phenylenediamine,N-(1-methylheptyl)-N′-phenyl-p-phenylenediamine,N-cyclohexyl-N′-phenyl-p-phenylenediamine,4-(p-toluenesulfamoyl)diphenylamine,N,N′-dimethyl-N,N′-di-sec-butyl-p-phenylenediamine, diphenylamine,N-allyidiphenylamine, 4-isopropoxydiphenylamine,N-phenyl-1-naphthylamine, N-(4-tert-octylphenyl)-1-naphthylamine,N-phenyl-2-naphthylamine, octylated di-phenylamine, for examplep,p′-di-tert-octyldiphenylamine, 4-n-butylaminophenol,4-butyrylaminophenol, 4-nonanoylamino-phenol, 4-dodecanoylaminophenol,4-octadecanoylaminophenol, bis(4-methoxyphenyl)amine,2,6-di-tert-butyl-4-dimethylaminomethylphenol,2,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylmethane,N,N,N′,N′-tetramethyl-4,4′-diaminodiphenylmethane,1,2-bis[(2-methylphenyl)amino]ethane, 1,2-bis(phenylamino)propane,(o-tolyl)biguanide, Bis[4-(1′,3′-dimethylbutyl)phenyl]amine,tert-octylated N-phenyl-1-naphthylamine, a mixture of mono- anddialkylated tert-butyl/tert-octyldiphenylamines, a mixture of mono- anddialkylated nonyidiphenylamines, a mixture of mono- and dialkylateddodecyldiphenylamines, a mixture of mono- and dialkylatedisopropyl/isohexyldiphenylamines, a mixture of mono- und dialkylatedtert-butyldiphenylamines,2,3-di-hydro-3,3-dimethyl-4H-1,4-benzothiazine, phenothiazine, a mixtureof mono- und dialkylated tert-butyl/tert-octylphenothiazines, a mixtureof mono- und dialkylated tert-octyl-phenothiazines, N-allylphenothiazin,N,N,N′,N′-tetraphenyl-1,4-diaminobut-2-ene,N,N-bis(2,2,6,6-tetramethyl-piperid-4-yl-hexamethylenediamine,bis(2,2,6,6-tetramethylpiperid-4-yl)sebacate,2,2,6,6-tetramethylpiperidin-4-one, 2,2,6,6-tetramethylpiperidin-4-ol.

2. UV Absorbers and Light Stabilisers

Nickel compounds, for example nickel complexes of2,2′-thio-bis-[4-(1,1,3,3-tetra-methylbutyl)phenol], such as the 1:1 or1:2 complex, with or without additional ligands such as n-butylamine,triethanolamine or N-cyclohexyldiethanolamine, nickeldibutyldithiocarbamate, nickel salts of the monoalkyl esters, e.g. themethyl or ethyl ester, of 4-hydroxy-3,5-di-tert-butylbenzylphosphonicacid, nickel complexes of ketoximes, e.g. of 2-hydroxy-4-methylphenylundecylketoxime, nickel complexes of1-phenyl-4-lauroyl-5-hydroxypyrazole, with or without additionalligands.

3. Metal deactivators, for example N,N′-diphenyloxamide,N-salicylal-N′-salicyloyl hydrazine, N,N′-bis(salicyloyl) hydrazine,N,N′-bis(3,5-di-tert-butyl-4-hydroxy-phenylpropionyl) hydrazine,3-salicyloylamino-1,2,4-triazole, bis(benzylidene)-oxalyl dihydrazide,oxanilide, isophthaloyl dihydrazide, sebacoyl bisphenyl-hydrazide,N,N′-diacetyladipoyl dihydrazide, N,N′-bis(salicyloyl)oxalyldihydrazide, N,N′-bis(salicyloyl)thiopropionyl dihydrazide.

4. Phosphites and phosphonites, for example triphenyl phosphite,diphenyl alkyl phosphites, phenyl dialkyl phosphites, tris(nonylphenyl)phosphite, trilauryl phosphite, trioctadecyl phosphite, distearylpentaerythritol diphosphite, tris(2,4-di-tert-butylphenyl) phosphite,diisodecyl pentaerythritol diphosphite, bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite,bis(2,6-di-tert-butyl-4-methylphenyl)-pentaerythritol diphosphite,diisodecyloxypentaerythritol diphosphite,bis(2,4-di-tert-butyl-6-methylphenyl)pentaerythritol diphosphite,bis(2,4,6-tris(tert-butylphenyl)pentaerythritol diphosphite, tristearylsorbitol triphosphite, tetrakis(2,4-di-tert-butylphenyl)4,4′-biphenylene diphosphonite,6-isooctyloxy-2,4,8,10-tetra-tert-butyl-12H-dibenz[d,g]-1,3,2-dioxaphosphocin,6-fluoro-2,4,8,10-tetra-tert-butyl-12-methyl-dibenz[d,g]-1,3,2-dioxaphosphocin,bis(2,4-di-tert-butyl-6-methylphenyl)methylphosphite,bis(2,4-di-tert-butyl-6-methylphenyl)ethylphosphite.

5. Hydroxylamines, for example, N,N-dibenzylhydroxylamine,N,N-diethylhydroxylamine, N,N-dioctylhydroxylamine,N,N-dilaurylhydroxylamine, N,N-ditetradecylhydroxylamine,N,N-dihexadecylhydroxylamine, N,N-dioctadecylhydroxylamine,N-hexadecyl-N-octadecylhydroxylamine,N-heptadecyl-N-octadecylhydroxylamine, N,N-dialkylhydroxylamine derivedfrom hydrogenated tallow amine.

6. Nitrones, for example, N-benzyl-alpha-phenyl-nitrone,N-ethyl-alpha-methylnitrone, N-octyl-alpha-heptyl-nitrone,N-lauryl-alpha-undecyl-nitrone, N-tetradecyl-alpha-tridecyl-nitrone,N-hexadecyl-alpha-pentadecyl-nitrone,N-octadecyl-alpha-heptadecyl-nitrone,N-hexadecyl-alpha-heptadecyl-nitrone,N-ocatadecyl-alpha-pentadecyl-nitrone,N-heptadecyl-alpha-heptadecyl-nitrone,N-octadecyl-alpha-hexadecyl-nitrone, nitrone derived fromN,N-dialkylhydroxylamine derived from hydrogenated tallow amine.

7. Thiosynergists, for example, dilauryl thiodipropionate or distearylthiodipropionate.

8. Peroxide scavengers, for example esters of β-thiodipropionic acid,for example the lauryl, stearyl, myristyl or tridecyl esters,mercaptobenzimidazole or the zinc salt of 2-mercaptobenzimidazole, zincdibutyldithiocarbamate, dioctadecyl disulfide, pentaerythritoltetrakis(β-dodecylmercapto)propionate.

9. Basic co-stabilisers, for example, melamine, polyvinylpyrrolidone,dicyandiamide, triallyl cyanurate, urea derivatives, hydrazinederivatives, amines, polyamides, polyurethanes, alkali metal salts andalkaline earth metal salts of higher fatty acids for example calciumstearate, zinc stearate, magnesium behenate, magnesium stearate, sodiumricinoleate and potassium palmitate, antimony pyrocatecholate or tinpyrocatecholate.

10. Nucleating agents, for example, inorganic substances such as talcum,metal oxides such as titanium dioxide or magnesium oxide, phosphates,carbonates or sulfates of, preferably, alkaline earth metals; organiccompounds such as mono- or polycarboxylic acids and the salts thereof,e.g. 4-tert-butylbenzoic acid, adipic acid, diphenylacetic acid, sodiumsuccinate or sodium benzoate; polymeric compounds such as ioniccopolymers (“ionomers”).

11. Fillers and reinforcing agents, for example, calcium carbonate,silicates, glass fibres, glass bulbs, asbestos, talc, kaolin, mica,barium sulfate, metal oxides and hydroxides, carbon black, graphite,wood flour and flours or fibers of other natural products, syntheticfibers.

12. Other additives, for example, plasticisers, lubricants, emulsifiers,pigments, rheology additives, catalysts, flow-control agents, opticalbrighteners, flameproofing agents, antistatic agents and blowing agents.

13. Benzofuranones and indolinones, for example those disclosed in U.S.Pat. No. 4,325,863, U.S. Pat. No. 4,338,244, U.S. Pat. No. 5,175,312,U.S. Pat. No. 5,216,052, U.S. Pat. No. 5,252,643, DE-A-4316611,DE-A-4316622, DE-A-4316876, EP-A-0589839 or EP-A-0591102 or3-[4-(2-acetoxyethoxy)phenyl]-5,7-di-tert-butyl-benzofuran-2-one,5,7-di-tert-butyl-3-[4-(2-stearoyloxyethoxy)phenyl]benzofuran-2-one,3,3′-bis[5,7-di-tert-butyl-3-(4-[2-hydroxyethoxy]phenyl)benzofuran-2-one],5,7-di-tert-butyl-3-(4-ethoxyphenyl)benzofuran-2-one,3-(4-acetoxy-3,5-dimethylphenyl)-5,7-di-tert-butyl-benzofuran-2-one,3-(3,5-dimethyl-4-pivaloyloxyphenyl)-5,7-di-tert-butyl-benzofuran-2-one.

The weight ratio of the total amount of components (I) and (II) andoptionally (X-1) and/or (X-2) to the total amount of the conventionaladditives can be, for example, 100:1 to 1:100.

The example below illustrates the invention in greater detail. Allpercentages and parts are by weight, unless stated otherwise.

Stabilizers used in the following Example 1:

Compound (A-1-b):

(TINUVIN 765 (RTM))

Compound (B-2-a):(CHIMASSORB 119 (RTM))

EXAMPLE I Light Stabilization of Polypropylene Homopolymer Films

100 parts of unstabilized polypropylene powder (melt flow index: 2.4g/10 minutes at 230° C. and 2160 g) are homogenized at 200° C. for 10minutes in a Brabender plastograph with 0.05 parts of pentaerythrityltetrakis{3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate}, 0.05 parts oftris{2,4-di-tert-butylphenyl} phosphite, 0.1 parts of Ca stearate, 0.25parts of titanium dioxide (anatase) and the light stabilizer systemindicated in Table 1. The material thus obtained is compression moldedin a laboratory press between two aluminum foils for 6 min at 260° C. toa 0.5 mm thick film which is cooled immediately to room temperature in awater-cooled press. Samples of 60 mm×25 mm are cut out of these 0.5 mmfilms and are exposed in a WEATHER-OMETER Ci 65 (black panel temperature63±2° C., without water-spraying).

Periodically, these samples are removed from the exposure apparatus andtheir carbonyl content is measured with an infrared spectrophotometer.The exposure time corresponding to formation of a carbonyl absorbance of0.1 in hours (T_(0.1)) is a measure for the efficiency of the stabilizersystem.

The synergistic effect of two coadditivs ((α) and (β)) is determined bya comparison of the calculated T_(0.1) value with the actually measuredT_(0.1) value. The T_(0.1) values are calculated on the basis of theadditivity law (B. Ranby and J. F. Rabek; Photodegradation,Photo-oxidation and Photostabilization of Polymers, Principles andApplications, John Wiley & Sons, London, New York, Sydney, Toronto,1975, pages 418 and 419) according to the following equation:${{Expected}\quad{stabilizing}\quad{activity}} = \frac{\begin{matrix}{{{Stabilizing}\quad{activity}\quad{of}\quad 100\quad\%\quad(\alpha)} +} \\{{{stabilizing}\quad{activity}\quad{of}\quad 100\quad\%\quad(\beta)}\quad}\end{matrix}}{2}$

There is a synergistic effect for the two coadditivs in question, whenT_(0.1 measured)>T_(0.1 calculated). TABLE 1 Light stabilizer systemT_(0.1) (h) (measured) $\begin{matrix}{\frac{{\left( T_{0.1} \right)\alpha} + {\left( T_{0.1} \right)\beta}}{2}(h)} \\\left( {= {T_{0.1}\quad{calculated}}} \right)\end{matrix}\quad$ without 390 0.2% of Compound (A-1-b) 4630 0.2% ofCompound (B-2-a) 2460 0.1% of Compound (A-1-b) + >5475 3545 0.1% ofCompound (B-2-a)

The combination of the compounds (A-1-b) and (B-2-a) shows a synergisticeffect.

1. A stabilizer mixture containing (I) one sterically hindered aminecompound selected from the group consisting of the classes (α-1), (α-2),(α-3), (α-4) and (α-5); and (II) one sterically hindered amine compoundselected from the group consisting of the classes (β-1), (β-2), (β-3)and (β-4); (α-1) a compound of the formula (A-1)

in which E₁ is C₁-C₄alkyl, m₁ is 1, 2 or 4, if m₁ is 1, E₂ isC₁-C₂₅alkyl, if m₁ is 2, E₂ is C₁-C₁₄alkylene or a group of the formula(α-I)

wherein E₃ is C₁-C₁₀alkyl or C₂-C₁₀alkenyl, E₄ is C₁-C₁₀alkylene, and E₅and E₆ independently of one another are C₁-C₄alkyl, cyclohexyl ormethylcyclohexyl, and if m₁ is 4, E₂ is C₄-C₁₀alkanetetrayl; (α-2) acompound of the formula (A-2)

in which two of the radicals E₇ are —COO—(C₁-C₂₀alkyl), and two of theradicals E₇ are a group of the formula (α-II)

with E₈ having one of the meanings of E₁; (α-3) a compound of theformula (A-3)

in which E₉ is C₁-C₂₄alkyl, and E₁₀ has one of the meanings of E₁; (α-4)a compound of the formula (A-4)

wherein the radicals E₁₁ independently of one another have one of themeanings of E₁, and E₁₂ is hydrogen, C₁-C₁₂alkyl or C₁-C₁₂alkoxy; (ax-5)a compound of the formula (A-5)

wherein E₁₃ has one of the meanings of E₁, and E₁₄ is a group of theformula (a-III)

wherein the radicals E₁₅ independently of one another areC₂-C₁₂alkylene, and the radicals E₁₆ independently of one another areC₁-C₁₂alkyl or C₅-C₁₂cycloalkyl; (β-1) a compound of the formula (B-1)

in which R₁, R₃, R₄ and R₅ independently of one another are hydrogen,C₁-C₁₂alkyl, C₅-C₁₂cycloalkyl, C₁-C₄-alkyl-substituted C₅-C₁₂cycloalkyl,phenyl, phenyl which is substituted by —OH and/or C₁-C₁₀alkyl;C₇-C₉phenylalkyl, C₇-C₉phenylalkyl which is substituted on the phenylradical by —OH and/or C₁-C₁₀alkyl; or a group of the formula (b-I)

R₂ is C₂-C₁₈alkylene, C₅-C₇cycloalkylene orC₁-C₄alkylenedi(C₅-C₇cycloalkylene), or the radicals R₁, R₂ and R₃,together with the nitrogen atoms to which they are bonded, perform a 5-to 10-membered heterocyclic ring, or R₄ and R₅, together with thenitrogen atom to which they are bonded, form a 5- to 10-memberedheterocyclic ring, R₆ is C₁-C₄alkyl, and b₁ is a number from 2 to 50,with the proviso that at least one of the radicals R₁, R₃, R₄ and R₅ isa group of the formula (b-I); (β-2) a compound of the formula (B-2)

wherein R₇ and R₁₁ independently of one another are hydrogen orC₁-C₁₂alkyl, R₈, R₉ and R₁₀ independently of one another areC₂-C₁₀alkylene, and X₁, X₂, X₃, X₄, X₅, X₆, X₇ and X₈ independently ofone another are a group of the formula (b-II),

in which R₁₂ is hydrogen, C₁-C₁₂alkyl, C₅-C₁₂cycloalkyl,C₁-C₄alkyl-substituted C₅-C₁₂cycloalkyl, phenyl, —OH— and/orC₁-C₁₀alkyl-substituted phenyl, C₇-C₉phenylalkyl, C₇-C₉phenylalkyl whichis substituted on the phenyl radical by —OH and/or C₁-C₁₀alkyl; or agroup of the formula (b-I) as defined above, and R₁₃ has one of themeanings of R₆; (β-3) a compound of the formula (B-3)

in which R₁₄, R₁₅, R₁₆, R₁₇ and R₁₈ independently of one another are adirect bond or C₁-C₁₀alkylene, R₁₉ has one of the meanings of R₆, and b₂is a number from 1 to 50; (β-4) a product (B-4) obtainable by reacting aproduct, obtained by reaction of a polyamine of the formula (B-4-1) withcyanuric chloride, with a compound of the formula (B-4-2)

in which b′₃, b″₃ and b′″₃ independently of one another are a numberfrom 2 to 12, R₂₀ is hydrogen, C₁-C₁₂alkyl, C₅-C₁₂cycloalkyl, phenyl orC₇-C₉phenylalkyl, and R₂, has one of the meanings of R₆.
 2. A stabilizermixture according to claim 1, wherein component (I) is selected fromclass (α-1) and component (II) is selected from class (β-1); orcomponent (I) is selected from class (α-1) and component (II) isselected from class (β-2); or component (I) is selected from class (α-1)and component (II) is selected from class (β-3); or component (I) isselected from class (α-1) and component (II) is selected from class(β-4); or component (I) is selected from class (α-2) and component (II)is selected from class (β-1); or component (I) is selected from class(α-2) and component (II) is selected from class (β-2); or component (I)is selected from class (α-2) and component (II) is selected from class(β-3); or component (I) is selected from class (α-2) and component (II)is selected from class (β-4); or component (I) is selected from class(α-3) and component (II) is selected from class (β-1); or component (I)is selected from class (α-3) and component (II) is selected from class(β-2); or component (I) is selected from class (α-3) and component (II)is selected from class (β-3); or component (I) is selected from class(α-3) and component (II) is selected from class (β-4); or component (I)is selected from class (α-4) and component (II) is selected from class(β-1); or component (I) is selected from class (ax) and component (II)is selected from class (β-2); or component (I) is selected from class(α-4) and component (II) is selected from class (β-3); or component (I)is selected from class (α-4) and component (II) is selected from class(β-4); or component (I) is selected from class (α-5) and component (II)is selected from class (β-1); or component (I) is selected from class(α-5) and component (II) is selected from class (β-2); or component (I)is selected from class (α-5) and component (II) is selected from class(β-3); or component (I) is selected from class (α-5) and component (II)is selected from class (β-4).
 3. A stabilizer mixture according to claim1 wherein m₁ is 1, 2 or 4, if m₁ is 1 E₂ is C₁₂-C₂₀alkyl, if m₁ is 2, E₂is C₂-C₁₀alkylene or a group of the formula (a-I) E₃ is C₁-C₄alkyl, E₄is C₁-C₆alkylene, and E₅ and E₆ independently of one another areC₁-C₄alkyl, and if m₁ is 4, E₂ is C₄-C₈alkanetetrayl; two of theradicals E₇ are —COO—(C₁₀-C₁₅alkyl), and two of the radicals E₇ are agroup of the formula (a-II); E₉ is C₁₀-C₁₄alkyl; E₁₂ is C₁-C₄alkoxy; theradicals E₁₅ independently of one another are C₂-C₆alkylene, and theradicals E₁₆ independently of one another are C₁-C₄alkyl orC₅-C₈cycloalkyl; R₁ and R₃ independently of one another are a group ofthe formula (b-I), R₂ is C₂-C₈alkylene, R₄ and R₅ independently of oneanother are hydrogen, C₁-C₁₂alkyl, C₅-C₈cycloalkyl or a group of theformula (b-I), or the radicals R₄ and R₅, together with the nitrogenatom to which they are bonded, form a 5- to 10-membered heterocyclicring, and b₁ is a number from 2 to 25; R₇ and R₁, independently of oneanother are hydrogen or C₁-C₄alkyl, R₈, R₉ and R₁₀ independently of oneanother are C₂-C₄alkylene, and X₁, X₂, X₃, X₄, X₅, X₆, X₇ and X₈independently of one another are a group of the formula (b-II), R₁₂ ishydrogen, C₁-C₄alkyl, C₅-C₈cycloalkyl or a group of the formula (b-I);R₁₄, R₁₅, R₁₆, R₁₇ and R₁₈ independently of one another are a directbond or C₁-C₄alkylene, and b₂ is a number from 1 to 25; b′₃, b″₃ andb′″₃ independently of one another are a number from 2 to 4, and R₂₀ ishydrogen, C₁-C₄alkyl, C₅-C₈cycloalkyl, phenyl or benzyl.
 4. A stabilizermixture according to claim 1, wherein component (I) is a compound of theformula (A-1-a), (A-1-b), (A-1-c), (A-1-d), (A-2-a), (A-3-a), (A-4-a) or(A-5-a); and component (II) is a compound of the formula (B-1-a),(B-1-b), (B-1-c), (B-2-a), (B-3-a) or a product (B-4-a);

in which two of the radicals E₇ are —COO—C₁₃H₂₇ and two of the radicalsE₇ are

wherein b₁ is a number from 2 to 20;

wherein b₂ is a number from 1 to 20; a product (B-4-a) obtainable byreacting a product, obtained by reaction of a polyamine of the formula(B-4-1-a) with cyanuric chloride, with a compound of the formula(B-4-2-a).


5. A stabilizer mixture according to claim 4 wherein component (I) isthe compound of the formula (A-1-a), (A-1-b), (A-1-c), (A-1-d), (A-2-a),(A-3-a), (A-4-a) or (A-5-a); and component (II) is the compound of theformula (B-1-c) or (B-2-a).
 6. A stabilizer mixture according to claim 4wherein component (I) is the compound of the formula (A-1-b) andcomponent (II) is the compound of the formula (B-1-c); or whereincomponent (I) is the compound of the formula (A-1-b) and component (II)is the compound of the formula (B-2-a).
 7. A stabilizer mixtureaccording to claim 1 wherein E₁, E₈, E₁₀, E₁₁, E₁₃, R₆, R₁₃, R₁₉ and R₂₁are methyl.
 8. A stabilizer mixture according to claim 1, whichadditionally contains as a further component (X-1) a pigment or (X-2) anUV absorber or (X-3) a pigment and an UV absorber.
 9. A compositioncomprising an organic material subject to degradation induced by light,heat or oxidation and a stabilizer mixture according to claim
 1. 10. Acomposition according to claim 9 wherein the organic material is asynthetic polymer.
 11. A composition according to claim 9 wherein theorganic material is a polyolefin.
 12. A composition according to claim 9wherein the organic material is polyethylene, polypropylene, apolyethylene copolymer or a polypropylene copolymer.
 13. A compositionaccording to claim 9 wherein the organic material isacrylonitrile/butadiene/styrene (ABS).
 14. A method for stabilizing anorganic material against degradation induced by light, heat oroxidation, which comprises incorporating into the organic material astabilizer mixture according to claim 1.